CN111300922B - Polyimide flexible copper-clad plate - Google Patents
Polyimide flexible copper-clad plate Download PDFInfo
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- CN111300922B CN111300922B CN201910361675.1A CN201910361675A CN111300922B CN 111300922 B CN111300922 B CN 111300922B CN 201910361675 A CN201910361675 A CN 201910361675A CN 111300922 B CN111300922 B CN 111300922B
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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Abstract
The invention provides a preparation method of a polyimide flexible copper clad laminate, which comprises the following steps: adding polyimide and a heat-conducting filler into dimethylformamide, and stirring to uniformly mix to obtain polyimide glue solution; selecting a rolled copper foil, and coating a polyimide glue solution on the rough surface of one copper foil under the protection of inert gas; imidizing in a nitrogen protection oven; covering another copper foil with the same size on the polyimide glue solution to obtain a semi-finished product, and heating and laminating; and (3) placing the semi-finished product of the non-adhesive copper-clad plate in a muffle furnace, and heating under the protection of inert gas for treatment to obtain the polyimide flexible copper-clad plate. The two-layer flexible copper clad laminate provided by the invention has small dimensional change and is very stable, the formed polyimide layer has good adhesion with a copper foil, the polyimide layer has low moisture absorption rate and low dielectric coefficient, and the performance is excellent.
Description
Technical Field
The invention relates to the field of materials, in particular to a polyimide flexible copper clad laminate.
Background
Polyimide is a polymer having an imide ring (-CO-NH-CO-) in the main chain, and among them, a polymer having a phthalimide structure is most important. Polyimide is one of organic polymer materials with the best comprehensive performance, has the advantages of high temperature resistance, low dielectric constant, corrosion resistance and the like, has the high temperature resistance of over 400 ℃, has the long-term use temperature range of-200-300 ℃, and has very high insulating property. Polyimide is used as a special engineering material, has been widely applied to the fields of aviation, aerospace, microelectronics, nano-materials, liquid crystals, separation membranes, lasers and the like, and becomes an irreplaceable functional material with excellent comprehensive performance.
The Flexible Copper Clad Laminate (FCCL) is a substrate of a Flexible Printed Circuit (FPC) and mainly comprises two types, namely a three-layer flexible copper clad laminate (3L-FCCL) and a two-layer flexible copper clad laminate (2F-FCCL). The three-layer copper clad laminate is generally prepared by bonding a polyimide film or a polyester film with a copper foil through an adhesive, hot pressing and post-curing. The two layers of flexible copper clad laminates only consist of polyimide films and copper foils, and the preparation process comprises three methods, namely a coating method, a pressing method and a sputtering method. In recent years, as electronic products using Flexible Printed Circuit (FPC) are developed toward high density and miniaturization, the demand for a thinner and lighter two-layer flexible copper clad laminate is greatly increased. The two-layer flexible copper clad laminate has the advantages of high heat resistance, excellent dimensional stability and folding resistance, and avoids the use of halogen, tetrabromobisphenol A and other organic matters harmful to the environment and human bodies in the three-layer laminate. In the field of flexible printed circuit boards with high-precision wiring and high use stability, two layers of flexible copper clad plates are developed rapidly.
The preparation process of the polyimide material for the two-layer method and the corresponding flexible copper clad laminate generally comprises the steps of selecting a proper combination of dianhydride and diamine, synthesizing polyimide acid at normal temperature or low temperature, coating the polyamide acid on a copper foil, and then carrying out solvent removal and high-temperature imidization treatment to obtain the two-layer flexible copper clad laminate while converting the polyamide acid into the polyimide.
However, the current 2F-FCCL performance still cannot meet the requirement, and has a larger promotion space.
Disclosure of Invention
The technical problem is as follows: in order to solve the defects of the prior art, the invention provides a polyimide flexible copper clad laminate.
The technical scheme is as follows: the invention provides a preparation method of a polyimide flexible copper clad laminate, which comprises the following steps:
(1) adding polyimide and a heat-conducting filler into dimethylformamide, and stirring to uniformly mix to obtain polyimide glue solution;
(2) selecting a rolled copper foil with the thickness of 8-80 mu m and subjected to roughening treatment, and coating the polyimide glue solution obtained in the step (1) on the rough surface of one copper foil under the protection of inert gas; performing stage heat treatment in a nitrogen protection oven at 80 ℃, 120 ℃, 185 ℃, 220-260 ℃ and 350-380 ℃ for 5-10min respectively to perform imidization;
(3) covering another copper foil with the same size on the polyimide glue solution to obtain a semi-finished product, and heating to 290-320 ℃ for lamination;
(4) placing the semi-finished product of the non-adhesive copper-clad plate obtained in the step (3) in a muffle furnace, heating to 390-420 ℃, and treating for 50-80 min under the protection of inert gas to obtain a polyimide flexible copper-clad plate;
wherein the structural formula of the polyimide is shown as formula V:
the preparation method of the polyimide comprises the following steps:
(a) reacting the compound shown in the formula VI with the compound shown in the formula VII to obtain an intermediate shown in the formula VIII;
(b) VIII, reacting the intermediate to obtain a compound shown in a formula V;
the reaction formula is as follows:
the preparation method of the polyimide comprises the following steps:
(a) under the protection of nitrogen and at a certain temperature, stirring the compound shown in the formula VI and the compound shown in the formula VII in an organic solvent for reaction to obtain an intermediate shown in the formula VIII;
(b) adding a dehydrating agent and a catalyst, continuously stirring the intermediate shown as VIII at a certain temperature for reaction, cleaning, filtering and drying to obtain the compound shown as the formula V.
In the step (a), the organic solvent is one of N-methyl pyrrolidone, N-dimethyl acetamide or N, N-dimethyl formamide; the reaction temperature is 5-25 ℃.
In the step (b), the dehydrating agent is one or a mixture of more of trifluoroacetic anhydride, acetic anhydride, thionyl chloride or an organic silicon compound; the molar ratio of the dehydrating agent to the compound VII is 3: 1-5: 1; the catalyst is one or a mixture of triethylamine and pyridine, and the molar ratio of the catalyst to the compound VII is 2: 1-4: 1; the reaction temperature is 40-60 ℃.
In the step (1), the heat-conducting filler is one or more of aluminum oxide, aluminum nitride, boron nitride and silicon carbide.
In the step (1), the weight percentage of polyimide in the polyimide glue solution is 12-20%, and the weight percentage of the filler in the polyimide glue solution is 5-10%.
In the step (2), the thickness of the polyimide glue solution coating layer is 8-15 μm.
In the step (3), the laminating pressure is 23-27 Mpa, and the laminating time is 50-100 min.
Has the advantages that: the two-layer flexible copper clad laminate provided by the invention has small dimensional change and is very stable, the formed polyimide layer has good adhesion with a copper foil, the polyimide layer has low moisture absorption rate and low dielectric coefficient, and the performance is excellent.
Detailed Description
The present invention is further explained below.
In the following examples, the reaction scheme is as follows:
example 1
The preparation method of the low dielectric polyimide comprises the following steps:
(1) under the protection of nitrogen and at a certain temperature, stirring the compound shown in the formula VI and the compound shown in the formula VII in an organic solvent for reaction to obtain an intermediate shown in the formula VIII; the organic solvent is N-methyl pyrrolidone; the reaction temperature is 15 ℃;
(2) adding a dehydrating agent and a catalyst, continuously stirring the intermediate shown in the formula VIII at a certain temperature for reaction, cleaning, filtering and drying to obtain a compound shown in the formula V; the dehydrating agent is trifluoroacetic anhydride; the molar ratio of the dehydrating agent to the compound VII is 4: 1; the catalyst is triethylamine, and the molar ratio of the catalyst to the compound VII is 3: 1; the reaction temperature was 50 ℃.
Evaluation method of polymer molecular structure: fourier Infrared Spectroscopy (FT-IR): the prepared PI film is carried out on an infrared spectrometer (Bruker Tensor-27, Germany);
the infrared spectrum of the polyimide having a polymerization degree of 1 prepared in example 1 shows: wave number 1764cm-1And 1711cm-1, respectively shows asymmetric and symmetric stretching peaks of carbonyl C ═ O on polyimide ring, 1361cm-1Belongs to the C-N stretch peak on the imide ring, 754cm-1Belonging to the C ═ O flexural vibration absorption peak on the imide ring, 1622cm-1Corresponding to the characteristic peaks of the benzene rings.
Example 2
The preparation method of the low dielectric polyimide comprises the following steps:
(1) under the protection of nitrogen and at a certain temperature, stirring the compound shown in the formula VI and the compound shown in the formula VII in an organic solvent for reaction to obtain an intermediate shown in the formula VIII; the organic solvent is N, N-dimethylacetamide; the reaction temperature is 5 ℃;
(2) adding a dehydrating agent and a catalyst, continuously stirring the intermediate shown in the formula VIII at a certain temperature for reaction, cleaning, filtering and drying to obtain a compound shown in the formula V; the dehydrating agent is acetic anhydride; the molar ratio of the dehydrating agent to the compound VII is 5: 1; the catalyst is pyridine, and the molar ratio of the catalyst to the compound VII is 4: 1; the reaction temperature was 40 ℃.
Example 3
The preparation method of the low dielectric polyimide comprises the following steps:
(1) under the protection of nitrogen and at a certain temperature, stirring the compound shown in the formula VI and the compound shown in the formula VII in an organic solvent for reaction to obtain an intermediate shown in the formula VIII; the organic solvent is N, N-dimethyl formyl; the reaction temperature is 25 ℃;
(2) adding a dehydrating agent and a catalyst, continuously stirring the intermediate shown in the formula VIII at a certain temperature for reaction, cleaning, filtering and drying to obtain a compound shown in the formula V; the dehydrating agent is thionyl chloride; the molar ratio of the dehydrating agent to the compound VII is 3: 1; the catalyst is triethylamine, and the molar ratio of the catalyst to the compound VII is 2: 1; the reaction temperature was 60 ℃.
Example 4
The preparation method of the polyimide flexible copper clad laminate comprises the following steps:
(1) adding the polyimide and the heat-conducting filler in the embodiment 1 into dimethylformamide, and stirring to uniformly mix to obtain polyimide glue solution; the heat conducting filler is silicon carbide. The weight percentage of the polyimide in the polyimide glue solution is 16 percent, and the weight percentage of the filler in the polyimide glue solution is 8 percent.
(2) Selecting a rolled copper foil with the thickness of 50 microns and subjected to roughening treatment, and coating the polyimide glue solution obtained in the step (1) on the rough surface of one copper foil under the protection of inert gas, wherein the thickness of the polyimide glue solution coating layer is 8-15 microns; performing stage heat treatment in a nitrogen protection oven at 80 ℃, 120 ℃, 185 ℃, 220-260 ℃ and 350-380 ℃ for 8min respectively to perform imidization;
(3) covering another copper foil with the same size on the polyimide glue solution to obtain a semi-finished product, and heating to 305 ℃ for lamination; laminating pressure is 25Mpa, and laminating time is 75 min;
(4) and (4) placing the semi-finished product of the non-adhesive copper-clad plate obtained in the step (3) in a muffle furnace, heating to 405 ℃, and treating for 65min under the protection of inert gas to obtain the polyimide flexible copper-clad plate.
Example 5
The preparation method of the polyimide flexible copper clad laminate comprises the following steps:
(1) adding the polyimide and the heat-conducting filler of the embodiment 2 into dimethylformamide, and stirring to uniformly mix to obtain polyimide glue solution; the heat conducting filler is alumina. The weight percentage of the polyimide in the polyimide glue solution is 12 percent, and the weight percentage of the filler in the polyimide glue solution is 5 percent.
(2) Selecting a rolled copper foil with the thickness of 50 microns and subjected to roughening treatment, and coating the polyimide glue solution obtained in the step (1) on the rough surface of one copper foil under the protection of inert gas, wherein the thickness of the polyimide glue solution coating layer is 8-15 microns; performing stage heat treatment in a nitrogen protection oven at 80 ℃, 120 ℃, 185 ℃, 220-260 ℃ and 350-380 ℃ for 5min respectively to perform imidization;
(3) covering another copper foil with the same size on the polyimide glue solution to obtain a semi-finished product, and heating to 290 ℃ for laminating; the laminating pressure is 27Mpa, and the laminating time is 100 min;
(4) and (4) placing the semi-finished product of the non-adhesive copper-clad plate obtained in the step (3) in a muffle furnace, heating to 390 ℃, and treating for 80min under the protection of inert gas to obtain the polyimide flexible copper-clad plate.
Example 6
The preparation method of the polyimide flexible copper clad laminate comprises the following steps:
(1) adding the polyimide and the heat-conducting filler of the embodiment 3 into dimethylformamide, and stirring to uniformly mix to obtain polyimide glue solution; the heat conducting filler is boron nitride. The weight percentage of the polyimide in the polyimide glue solution is 20 percent, and the weight percentage of the filler in the polyimide glue solution is 10 percent.
(2) Selecting a rolled copper foil with the thickness of 50 microns and subjected to roughening treatment, and coating the polyimide glue solution obtained in the step (1) on the rough surface of one copper foil under the protection of inert gas, wherein the thickness of the polyimide glue solution coating layer is 8-15 microns; performing stage heat treatment in a nitrogen protection oven at 80 ℃, 120 ℃, 185 ℃, 220-260 ℃ and 350-380 ℃ for 10min respectively to perform imidization;
(3) covering another copper foil with the same size on the polyimide glue solution to obtain a semi-finished product, and heating to 320 ℃ for laminating; the laminating pressure is 23Mpa, and the laminating time is 50 min;
(4) and (4) placing the semi-finished product of the non-adhesive copper-clad plate obtained in the step (3) in a muffle furnace, heating to 420 ℃, and treating for 5min under the protection of inert gas to obtain the polyimide flexible copper-clad plate.
Example 7 testing of the product Properties of examples 4 to 6
The results are shown in Table 1.
The test method is as follows:
dimensional stability: testing according to IPC-TM-650-2.2.4 method.
Testing according to IPC-TM-650-2.6.2 method.
Peel strength: the test was carried out according to the IPC-TM-650-2.4.9 method.
Dip soldering resistance: the test was carried out according to the IPC-TM-650-2.4.13 method.
Other tests are also routine in the art.
Claims (9)
1. A preparation method of a polyimide flexible copper clad laminate is characterized by comprising the following steps: the method comprises the following steps:
(1) adding polyimide and a heat-conducting filler into dimethylformamide, and stirring to uniformly mix to obtain polyimide glue solution;
(2) selecting a rolled copper foil with the thickness of 8-80 mu m and subjected to roughening treatment, and coating the polyimide glue solution obtained in the step (1) on the rough surface of one copper foil under the protection of inert gas; performing stage heat treatment in a nitrogen protection oven at 80 ℃, 120 ℃, 185 ℃, 220-260 ℃ and 350-380 ℃ for 5-10min respectively to perform imidization;
(3) covering another copper foil with the same size on the polyimide glue solution to obtain a semi-finished product, and heating to 290-320 ℃ for lamination;
(4) placing the semi-finished product of the non-adhesive copper-clad plate obtained in the step (3) in a muffle furnace, heating to 390-420 ℃, and treating for 50-80 min under the protection of inert gas to obtain a polyimide flexible copper-clad plate;
wherein the structural formula of the polyimide is shown as formula V:
2. the preparation method of the polyimide flexible copper clad laminate according to claim 1, wherein the preparation method comprises the following steps: the preparation method of the polyimide comprises the following steps:
(a) reacting the compound shown in the formula VI with the compound shown in the formula VII to obtain an intermediate shown in the formula VIII;
(b) VIII, reacting the intermediate to obtain a compound shown in a formula V;
the reaction formula is as follows:
3. the preparation method of the polyimide flexible copper clad laminate according to claim 2, wherein the preparation method comprises the following steps: the preparation method of the polyimide comprises the following steps:
(a) under the protection of nitrogen and at a certain temperature, stirring the compound shown in the formula VI and the compound shown in the formula VII in an organic solvent for reaction to obtain an intermediate shown in the formula VIII;
(b) adding a dehydrating agent and a catalyst, continuously stirring the intermediate shown as VIII at a certain temperature for reaction, cleaning, filtering and drying to obtain the compound shown as the formula V.
4. The preparation method of the polyimide flexible copper clad laminate according to claim 3, wherein the preparation method comprises the following steps: in the step (a), the organic solvent is one of N-methyl pyrrolidone, N-dimethyl acetamide or N, N-dimethyl formamide; the reaction temperature is 5-25 ℃.
5. The preparation method of the polyimide flexible copper clad laminate according to claim 3, wherein the preparation method comprises the following steps: in the step (b), the dehydrating agent is one or a mixture of more of trifluoroacetic anhydride, acetic anhydride, thionyl chloride or an organic silicon compound; the molar ratio of the dehydrating agent to the compound VII is 3: 1-5: 1; the catalyst is one or a mixture of triethylamine and pyridine, and the molar ratio of the catalyst to the compound VII is 2: 1-4: 1; the reaction temperature is 40-60 ℃.
6. The preparation method of the polyimide flexible copper clad laminate according to claim 1, wherein the preparation method comprises the following steps: in the step (1), the heat-conducting filler is one or more of aluminum oxide, aluminum nitride, boron nitride and silicon carbide.
7. The preparation method of the polyimide flexible copper clad laminate according to claim 1, wherein the preparation method comprises the following steps: in the step (1), the weight percentage of polyimide in the polyimide glue solution is 12-20%, and the weight percentage of the filler in the polyimide glue solution is 5-10%.
8. The preparation method of the polyimide flexible copper clad laminate according to claim 1, wherein the preparation method comprises the following steps: in the step (2), the thickness of the polyimide glue solution coating layer is 8-15 μm.
9. The preparation method of the polyimide flexible copper clad laminate according to claim 1, wherein the preparation method comprises the following steps: in the step (3), the laminating pressure is 23-27 Mpa, and the laminating time is 50-100 min.
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| KR910000832A (en) * | 1988-06-28 | 1991-01-30 | 랄프 챨스 메더스트 | Low dielectric constant and low moisture absorption polyimide and copolyimide for interlevel dielectric and substrate coatings |
| CN103113587B (en) * | 2013-03-14 | 2015-06-17 | 华威聚酰亚胺有限责任公司 | Flexible hyperbranched semi-interpenetrating fluorinated polysiloxane polyimide film and preparation method thereof |
| CN104760369B (en) * | 2015-04-23 | 2016-08-24 | 东华大学 | A kind of fluorinated polyimide copper coated foil plate and preparation method thereof |
| JP6971580B2 (en) * | 2016-02-12 | 2021-11-24 | 株式会社カネカ | Multilayer polyimide film and flexible metal-clad laminate |
| CN107599588A (en) * | 2016-07-11 | 2018-01-19 | 江阴汉姆应用界面有限公司 | A kind of preparation method of polyimides flexibility coat copper plate |
| CN109627470B (en) * | 2018-11-09 | 2021-04-20 | 株洲时代华鑫新材料技术有限公司 | Preparation method of low dielectric polyimide film |
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